CN1836058A

CN1836058A - New metal strip product

Info

Publication number: CN1836058A
Application number: CNA2004800231369A
Authority: CN
Inventors: 安纳·胡尔廷斯蒂根贝里; 米卡埃尔·舒伊斯凯
Original assignee: Sandvik Intellectual Property AB
Current assignee: Sandvik Intellectual Property AB
Priority date: 2003-08-12
Filing date: 2004-08-09
Publication date: 2006-09-20
Also published as: WO2005014876A1; US20050064214A1; SE0302207L; US20070072008A1; JP2007502364A; US20070042204A1; CN1836059A; CA2534291A1; JP2007502363A; US7147932B2; US7147931B2; KR20060056987A; SE0302207D0; WO2005014877A1; US20070042205A1; EP1656466A1; KR20060057608A; US20050064215A1; SE527180C2; EP1664366A1

Abstract

The present invention relates to a coated steel strip product with a dense and hard abrasion resistant coating on one side or both sides of said strip. The thickness of said coating is in total maximally 25 m, the hardness of said coating is at least 600 HV and the tensile strength of the steel strip substrate is at least 1200 MPa. The coating is preferably applied by electron beam evaporation and the coating may be, e.g., of A1203. The coated metal strip is useful for the manufacturing of doctor and coater blades for paper and printing industry.

Description

New metal strip product

The present invention relates generally to and have very hard and new coated steel strip material dense coating.Relate to the method for the above-mentioned coated steel strip of preparation under continuous coil type technology simultaneously, this will cause hard and dense coating sticks on the metallic strip substrate admirably.Especially, the present invention relates to coated steel strip, it is applicable to coater and scraper to such an extent as to its hard coat has fabulous adhesivity.

Background technology of the present invention and prior art

Scraper and coater blade all are used for paper-making industry and press, in order to respectively from rotation roller scraping paper and printing ink.Xiang Guan problem often comes across the wearing and tearing of roller and coater or scraper therewith.Coater and scraper are normally prepared by the sclerosis steel band.A usual way of the problem that reduces wear is after blade manufactures the geometrical shape of final coater or scraper, uses abrasion-resistant coatings on steel blade.For this reason, between base material and abrasion-resistant coatings, adopt with nickel dam as bonding coat usually.

Therefore, it is known can adopting abrasion-resistant coatings, but to find have cost benefit and eco-friendly, can satisfy required method for quality and also have difficulties.The cost that has the coater of the abrasion-resistant coatings of using or scraper is very high at present.In addition, also higher at the cost of Printing industry or the quality problems that take place between the usage period in the paper mill.Because therefore cost needs successive coil type coating processes, it preferably is integrated in the production of steel band.In addition, because quality, employing is favourable with the dense coating that base material has good adhesion.From becoming originally, without any need for independent bonding coat, then will be its another advantage if abrasion-resistant coatings has fabulous adhesivity.

For realizing the service quality of coater or scraper finished product, dense coating needs good adhesivity.Poor adhesion or porous or coarse coating will have problems between the usage period in coater blade or scraper, and for example, coating begins to peel off, or particulate or small pieces breakage, or crack problem.Generally speaking, from quality with become originally, this is unacceptable, because this class problem of scraper will cause printing quality poor, or need be in the paper mill frequent shut-down, replaces the coater blade of damaging.In processing industry, as the paper mill, each shut-down is all expensive and must avoid.

That uses at present has a several frequently seen layer manufacturing method that is coated with, and also has several dissimilar coatings using.Can mention having as an example:

Ceramic coating is usually by being added with TiO ₂And/or ZrO ₂Al ₂O ₃Form.Usually adopt the method for thermospray to use such coating, the case description of this method is wherein used ceramic coating along an edge of scraper in US-A-6431066 for example.In EP-B-758026, described the other method example, wherein in comprising the quite complicated continuous processing of thermospray, adopted several coating steps, used improved abrasion resistant coating along an edge.Generally there are some main defectives in heat spraying method.Formed coating is coarse, and this just means after coating and must polish or other further processing the surface.Hot spray coating also comprises highly porous usually, this means the dense coating that generally can not obtain to approach.In addition, the thickness of hot spray coating is all quite thick usually.Under the situation of coater and scraper, the thickness range of ceramic coating is generally 20-100 μ m.During use, thick and coarse coating has increased and has formed crackle or the particulate risk from surfacial spalling.As a rule, must use expensive nickel or nickelalloy as the adhesivity of bonding coat with the raising ceramic coating.

Metallic paint is made up of pure nickel or chromium usually, or is the compound form such as nickel phosphide.Usually adopt the method for spraying plating, especially the method for EFI plating is used such metallic paint.There are some defectives in the method for EFI plating, main one be exactly be difficult to obtain the uniform coating of thickness and the coating adhesivity relatively poor.And spraying plating process is not environmentally friendly, and on the contrary, these technologies produce environmental problem usually.

Composite coating for example comprises the nickel coating of abrasion-resistant particles such as SiC.In WO02/46526, described the example of this method,, in several steps, used different layers, and at least one above-mentioned steps, add abrasion-resistant particles wherein at the continuous processing that is used for the electrolytic nickel coating.Also there are some defectives in this method, and is identical substantially with the defective of above-mentioned EFI plating, but also the defective of existence is, nickel is as bonding coat to a great extent, and this just means that coating is very expensive.

Therefore, the method described in the above-mentioned example can not be used for the present invention.

Therefore, main purpose of the present invention provides hard and anti abrasive metallizing band, and described metal strip has improved adhesivity between dense coating and base material.

Another object of the present invention is to obtain to have cost-efficient coating in the coil type technology continuously, and described continuous coil type technology is integrated in the production of steel band.

Another object of the present invention is to provide the coated steel strip product of the tight zone with abrasion-resistant coatings, so that prepare the coater and the scraper of described material.

Another object of the present invention provide with coil type technology in the continuous coated directly related method for preparing scraper or coater blade, described coil type technology is included in the strip production line, need not any further manufacturing step in single blade manufacturing.

Another object of the present invention is to obtain thickness coating as far as possible uniformly.

By coated steel product as claimed in claim 1 is provided, can obtain above-mentioned surprisingly and other purposes.Defined further preferred embodiment in the dependent claims.

The accompanying drawing summary

Figure 1 shows that the cross sectional representation of metal strip according to an embodiment of the invention.

Figure 2 shows that cross sectional representation according to the metal strip of second embodiment of the invention.

Figure 3 shows that the sketch chart of the production line that is used to make metallizing band of the present invention.

Detailed Description Of The Invention

Be applicable to fine and close and hard wear resistant damage finished product coating, the hardened steel band forms and scrape The application of cutter and coater blade is as being used as rotogravure printing or flexible intaglio plate (flexogravure) The scraper of printing, or in papermaking, be used as the coater blade of scraping paper, or in papermaking, be used for pleat The fold blade of wadding. Wearing and tearing all can appear on the blade in these all application usually, institute Stating wearing and tearing stems from and the contacting or come from the paper that comprises the mineral that wear and tear of roller. Suitable coating Should be with having good adhesion and anti abrasive dense coating, it is hard and have enough tough The property bearing service load and pressure during use, and can not present any easily crisp or damaged Trend.

For preventing the finished product wearing and tearing, applying product at least, one deck abrasion-resistant coatings is appropriate. Can adopt a side or two-sided coatings. From becoming originally to see that one-sided coating is preferred, should be as far as possible Be used, in the scraper in particular for flexible intaglio printing, one-sided coating can be kept usually To required useful life. But for blade application in worse condition, or need longer Service time the time, two-sided coatings then is preferred. Otherwise will have problems: for example, the edge is not The edge generation plastic deformation of coated side, or pile up material along the edge of uncoated side, once in a while can It tears to name a person for a particular job from one, causes material to be torn by the part from the coater blade edge.

Method of the present invention is applicable to hard and fine and close wear-resistant shallow layer, described scumbling Layer is 25 μ m to the maximum in the gross thickness of each side, and general gross thickness is 20 μ m to the maximum, and is preferred maximum 15 μ m, or preferably be 12 μ m from the cost aspect to the maximum or even be 10 μ m to the maximum. If Apply thicker coating, adopt the multilayer that mostly is 10 layers most can obtain best cost performance, And each layer thickness is 0.1-15 μ m, is 0.1-10 μ m suitably, more suitably is 0.1-7 μ m, and is excellent Select 0.1-5 μ m and more preferably 0.1-3 μ m.

Speed with minimum 2.5 m/mins applies, and preferred minimum 5 m/mins, most preferably Minimum 10 m/mins.

Coating should have wearing and tearing and the shearing of enough mar proofs to bear processed material, Owing to economic cause and fragility/fragility, coating can not be too thick on the other hand. For the coater cutter The application of sheet and scraper, the thickness ratio between coating and the substrate material should 0.1%-12% it Between, be generally 0.1%-10%, and be generally 0.1%-7.5%, but most preferably be 0.1%-5%.

By depositing one deck dense oxide coating at least, can realize wearability, described dense oxide coating is Al ₂O ₃, TiO ₂, ZrO ₂Or these hopcalite forms, be preferably Al ₂O ₃-Ji form.As required, by in coating, adopting mixed oxide, can obtain required optimum hardness and toughness.This can obtain by co-evaporation of aluminum and other selected oxide compounds.Preferably can be co-evaporation of aluminum and other any oxide compounds, preferred TiO ₂And/or ZrO ₂Also can adopt multilayer, realizing the combination of oxide compound, thereby have different oxide compounds in maximum 10 layers, each layer and make hardness and toughness optimization by adopting.

Different with the above-mentioned abrasion-resistant coatings of substantially being made up of oxide compound is that other densifications and hard coating such as metallic coating also can be used for the present invention.If, then can adopt hard metallic coating, as pure substantially Cr for the preferred simple and cheap coating that reduces cost as much as possible.

Another change of the present invention is to adopt the carbide of transition metal and/or layer/coating of nitride such as TiN, TiC or CrN, in some cases also can with Al ₂O ₃, TiO ₂Or ZrO ₂Or these hopcalite forms, preferred Al ₂O ₃The oxide compound of base form combines.Have maximum 10 layers multilayer systems by employing, combine and the coating that exists can further strengthen the optimization of required hardness and toughness by several layers of different oxide compound and nitride.

In order to bear abrasion and the shearing force on coater or scraper, the hardness of shallow layer should be higher than 600HV, more suitably is higher than 700HV, preferably is higher than 800HV, most preferably is higher than 900HV.

The tolerance of each layer is bed thickness+/-10% to the maximum when width of steel band is 400mm to the maximum.This just means can obtain utmost point tighter tolerances, and this quality to precision between the usage period and product is favourable.Compare with spraying plating or thermospray, this has shown higher tolerance.For example, in plating, have so-called dog bone formula effect, this will cause the thickness difference on the coating.In this case, the variation of coating usually greater than bed thickness+/-50%.

Do not need any independent bonding coat, if but need technically, still the nickel metal can be used for wherein one deck, for example in order to strengthen toughness.Because the nickel metal is expensive, it only is used for extremely thin layer usually, is 0-2 μ m preferably, is preferably 0-1 μ m, most preferably is 0-0.5 μ m.Yet, any possible nickel metal layer all be not with base material adjacent the layer.

The description of substrate material to be coated

Material to be coated should have good basic physical strength, is suitable for the application of coater or scraper.Preferably, but it should be the hardened steel under sclerosis and tempered condition, or precipitation hardening steel, as disclosed alloy among the WO93/07303, it can obtain to be higher than the tensile strength of 1200MPa under final state, or preferably be higher than 1300MPa, or preferably be higher than 1400MPa, or even be higher than 1500MPa.If expection is applied to coater or scraper in corrosive environment, the chromium metal that also should add capacity so in this Steel Alloy is to have good basic erosion resistance.In this case, the content of Cr should be higher than 10wt%, or 11wt% at least, or preferred 12wt% at least.

This coating method can be applied to anyly be made and be the product of belt-like form by described types of steel alloy, and described steel band has good hot workability and can be cold-rolled to thin size.This alloy also should be able to easily be made coater and scraper in the manufacturing process that comprises as moulding, grinding, scraping, shearing, polishing, punch steps.The thickness of strip substrate is generally 0.015-5.0mm, is 0.03-3mm suitably.Be preferably 0.03-2mm, and 0.03-1.5mm more preferably.Whether the width of substrate material depended on before or after dissecing operation and applies.In addition, should preferably select to be suitable for described width further is machined to the width of coater or the final width of scraper.Therefore the width of substrate material be 1-1500mm in principle, is 1-1000mm suitably, or preferred 1-500mm, or even more preferably 5-500mm.Substrate material be 10-20000m with being of convenient length, be preferably 100-20000m.

The description of coating method

It can adopt various physics or the chemical vapor deposition methods that are used for this coated media and coating processes, as long as can provide continuously even and have adhering coating.The example of the deposition method that can mention has: chemical vapour deposition (CVD), organometallic chemical vapor deposition (MOCVD), physical vapor deposition (PVD) still especially preferably is used for electron beam evaporation (EB) deposition for the present invention as producing splash and evaporation by resistive heating, electron beam, induction, arc resistance or laser deposition method.Choose wantonly, electron beam evaporation can be by plasma exciatiaon further to guarantee hard and good quality dense coating.

For the present invention, its prerequisite is that coating method is to be integrated in the coil type strip production line.In coil type technology, hard coating is deposited by electron beam evaporation (EB).Multilayer if desired, then multiwalled forms and can obtain by online integrated several electron beam deposition chambers.The deposition of metallic coating should be 1 * 10 at peak pressure ^-2Mbar and do not add in the decompression of any reactant gas and carry out is to guarantee the being pure metal film basically.The deposition of metal oxide should be added with oxygen source as carrying out in the decompression of reactant gas in the sediment chamber.The dividing potential drop of oxygen should be in 1-100 * 10 ^-4In the scope of mbar.If obtain the coating of other types, carbide and/or nitride such as TiN, TiC or CrN as transition metal, or the mixture of itself and for example metal oxide, the condition during then applying should be adjusted to guarantee the formation of expecting compound according to the dividing potential drop of reactant gas.Under the situation of oxygen, can adopt as H ₂O, O ₂Or O ₃, but preferred O ₂As reactant gas.Under the situation of nitrogen, can adopt as N ₂, NH ₃Or N ₂H ₄, but preferred N ₂As reactant gas.Under the situation of carbon, any carbonaceous gas can be used as reactant gas, as CH ₄, C ₂H ₂Or C ₂H ₄The reactive electron beam evaporation process of all these all can be by excitation of plasma.

In order to obtain good adhesivity, various dissimilar cleanings have been adopted.At first, should be with the surface of appropriate means cleaned base material material removing all oil residues, otherwise will adverse influence be arranged to the efficient of coating processes, the adhesivity and the quality of coating.In addition, (native) oxide skin of nature as thin as a wafer that also must removal be present in the steel surface usually.This can finish the pre-treatment on surface by comprising preferably before the deposition of carrying out coating.Thereby in this coil type production line, first production stage is preferably the ion-assisted etching to metallic strip surface, with the good adhesion [referring to Fig. 3] that obtains first coating.

The description of embodiment of the present invention

Hereinafter with two embodiment of more detailed description embodiment of the present invention.First embodiment (Fig. 1) is included in the

coating

1,2 that is used for substrate material 3 in the whole width of steel band.This substrate material can be made by different alloys, as carbon steel or the hardenable stainless chromium steel of can hardening.Another embodiment (Fig. 2) comprises the coating 4 of steel band 5, and described steel band 5 has been dissectd and Edge Finish to width is substantially the twice of final coater blade width before coating processes.In coating procedure, major

opposing side

7,8 and narrow beside 9,10 all will apply, thereby obtain the complete coating of parcel scraping or cut edge 11,12.Suitably, beside 9,10 and slightly narrow major opposing side 7 are applied simultaneously.Given embodiment only is as illustrative example of the present invention, not as limitation of the present invention.

Substrate material should have the hardened of being suitable for to be formed, and this means:

The carbon of 0.1%-1.5%, the chromium of 0.001%-4%, the manganese of 0.01%-1.5%, the silicon of 0.01%-1.5%, maximum 1% nickel, the nitrogen of 0.001%-0.5%, surplus is essentially the hardened carbon steel of iron; Perhaps

The carbon of 0.1%-1.5%, the chromium of 10%-16%, the nickel of 0.001%-1%, the manganese of 0.01%-1.5%, the silicon of 0.01%-1.5%, maximum 3% molybdenum, the nitrogen of 0.001%-0.5%, surplus is essentially the hardened chromium steel of iron; Perhaps

The carbon of 0.001%-0.3%, the chromium of 10%-16%, the nickel of 4%-12%, the titanium of 0.1%-1.5%, the aluminium of 0.01%-1.0%, the molybdenum of 0.01%-6%, the copper of 0.001%-4%, the nitrogen of 0.001%-0.3%, the manganese of 0.01%-1.5%, the silicon of 0.01%-1.5%, surplus are essentially the precipitation hardening steel of iron.

Embodiment 1

The chemical constitution of substrate material is Sandvik grade of steel 20C2 and the 13C26 according to inside in the present embodiment, has following nominal basically and forms:

The carbon of Sandvik 20C2:1.0%, 1.4% chromium, 0.3% silicon and 0.3% manganese (weight percent);

The carbon of Sandvik 13C26:0.7%, 13% chromium, 0.4% silicon and 0.7% manganese (weight percent).

At first, prepare the substrate material of above-mentioned chemical constitution by common steel-making smelting technology.Then, be hot rolled to intermediate sizes, in several steps, carry out cold rollingly afterwards, between described rolling step, adopt a plurality of re-crystallization step, until the final thickness that reaches 0.2mm be the width of 400mm to the maximum.Then steel band is hardened and tempered to desired mechanical strength level, is at least 1200MPa according to the present invention.Adopt appropriate means to remove the surface of substrate material, in order to remove residual greasy dirt rolling and that cure operations produces.Then, apply processing starting from the continuous processing line of Abrollhaspel.The first step of coil type processing line connects the vacuum chamber of etching chamber or enters the mouth vacuum lock after can being, carries out ion-assisted etching therein, to remove the thin oxide layer on substrate material surface.Steel band enters electron beam (EB) evaporator room subsequently, carries out the deposition of oxide compound therein, in this example Al ₂O ₃Be selected as and treat deposition material.Usually deposit the oxide skin of 0.1-25 μ m.Preferred thickness is decided with the application scenario.Under this routine described situation, deposit the thickness of 2 μ m by using an electron beam (EB) evaporator room.After electron beam (EB) evaporation, coated steel strip material is coiled on the reeling machine subsequently by outlet vacuum chamber or outlet vacuum lock.This moment if required, coated steel strip material further can be processed as dissect, deburring, to obtain being used to make preferred final size of coater blade and edge situation.If carry out other coating along the edge of coater blade finished product, then can in the continuous coating processes that adopts electron beam (EB) evaporation, carry out, but also can adopt other technology, this is more favourable.Preferably, the other coating of carrying out along coater blade finished product edge is a same type with the coating that is applied on the strip material of the present invention.

The finished product in aforesaid example, just respectively through coating, thickness of strips is 0.2mm and has the thin Al of 2 μ m ₂O ₃The 20C2 of coating and 13C26 strip material have good coating adhesivity, therefore especially are suitable for making the scraper that is used for flexible intaglio printing or rotogravure.

Above-mentioned coil type electron beam evaporation process as shown in Figure 3.The first part of this production line is the Abrollhaspel 13 that is positioned at vacuum chamber 14, be online ion-assisted etching chamber 15 then, then be a series of eb evaporation chambers 16, the quantity of required eb evaporation chambers can be 1-10 and does not wait, and this is in order to obtain the required multiple coating structure of possibility.The water jacketed copper crucible 18 that all eb evaporation chambers 16 are equipped with electron beam gun 17 and are used to evaporate.Then be to be the outlet vacuum chamber 19 and the reeling machine 20 of coated steel strip material configuration after eb evaporation chambers, reeling machine is placed in the vacuum chamber 19.Vacuum chamber 14 and 19 also can replace with inlet vacuum lock and outlet vacuum lock system respectively.In following example, place Abrollhaspel 13 and reeling machine 20 outdoor.

Embodiment 2

The chemical ingredients of substrate material is the Sandvik grade of steel 20C according to inside in the present embodiment, has following nominal basically and forms:

The carbon of Sandvik 20C:1.0%, 0.2% chromium, 0.3% silicon and 0.4% manganese (weight percent).

At first, prepare substrate material by common steel-making smelting technology with above-mentioned chemical constitution.Then, be hot rolled to intermediate sizes, in several steps, carry out cold rollingly afterwards, adopt a plurality of re-crystallization step between the described rolling step, until the final thickness that reaches 0.45mm be the width of 400mm to the maximum.Then steel band is hardened and tempered to the mechanical strength level of requirement, according to the present invention for being higher than 1200MPa.Steel band is dissectd the width that becomes to be essentially final blade application width twice afterwards.According to present embodiment, final coater blade width is 100mm, therefore steel band is dissectd into wide 200-250mm.Dissect the back edge of steel band is handled, for example carried out scraping, grinding and polishing to reach the state and the profile of the coater blade application that is suitable for expecting.Afterwards, steel band is carried out coating processing with embodiment 1 all fours, equally can be with reference to figure 3.The finished product are coated steel strips as shown in Figure 2, and coating material is all identical with embodiment 1 with thickness.Coated steel strip can therefrom dissect to open and obtain two coated steel strips along section 6 now, and each all has state and the profile that is suitable for final coater blade application.The steel band that only keeps the final lengths that is cut into requirement in principle.

Described in the present embodiment the finished product, just through dissecing, Edge Finish and coating, having thickness is that 0.45mm, final slitted width are the band of 100mm, have the thin Al of 2 μ m of good adhesion ₂O ₃Coating.This product can be cut into required length, between 3 meters and 10 meters, is used as the coater blade in paper mill then, and need not carries out any further processing usually.If desired, it also can further be processed, and as other Edge Finish or along the other coating at edge, perhaps polishing or the like is to meet specific user's requirement.Other coating along the coater blade edge is preferably carried out in the continuous coating processes that adopts electron beam evaporation, but also can adopt other technologies.

Claims

1. coated steel strip product, have fine and close and hard abrasion-resistant coatings in one or two side of described steel band, it is characterized in that: described coating is applied directly on the steel band base material, the total thickness of described coating is 25 μ m to the maximum, the hardness of described coating is at least 600HV, and the tensile strength of steel band base material is at least 1200MPa.

2. product as claimed in claim 1 is characterized in that: the thickness of described steel band base material is 0.015-5.0mm.

3. product as claimed in claim 1 or 2 is characterized in that: described steel band base material is made by maybe can harden stainless chromium steel or precipitation hardening steel band of the carbon steel that can harden.

4. as each described product of claim 1-3, it is characterized in that: described coating is basically by Al ₂O ₃Make.

5. as each described product of claim 1-3, it is characterized in that: described coating is Al ₂O ₃And TiO ₂And/or ZrO ₂Mixture, main component is Al ₂O ₃

6. as each described product of claim 1-3, it is characterized in that: described coating is the metallic coating that contains Cr basically.

7. as each described product of claim 1-3, it is characterized in that: described coating is transition metal carbide or transition metal nitride, preferred TiN, TiC or CrN, the perhaps coating of its mixture.

8. the described product of arbitrary as described above claim is characterized in that: described coating has the most nearly 10 layers multilayered structure.

9. product as claimed in claim 8 is characterized in that: the thickness of each single layer is 0.1-15 μ m.

10. product as claimed in claim 9 is characterized in that: described coating has multilayered structure, and its each individual layer is Al ₂O ₃, TiO ₂Or ZrO ₂Or the different oxide coatings of its form of mixtures, and also can combine with nitride or the carbide lamella such as TiN and TiC if necessary, also can combine if further need with metallic coating such as Cr.

11. product as claimed in claim 10 is characterized in that: also exist at least one thickness to be up to the nickel dam of 2 μ m, this nickel dam and steel band base material are non-conterminous.

12. make the method for the described coated steel strip product of arbitrary as described above claim, it is characterized in that: in the continuous coil type technology in being contained in steel strip production line, employing comprises the electron beam evaporation of online etching chamber, produces described product with at least 2.5 meters/minutes speed.

13. be suitable for scraper or coater blade as paper-making industry and press, it comprises each described coated steel strip product as claim 1-11.

14. scraper as claimed in claim 13 or coater blade is characterized in that: its scraping and/or cutting beside also are coated with the application composition identical with major opposing side.

15. make method as each described scraper of claim 13-15 or coater blade, it is characterized in that: in the continuous coil type technology in being contained in steel strip production line, employing comprises the electron beam evaporation of online etching chamber, produce described blade with at least 2.5 meters/minutes speed, the width of steel band of described blade final scraper or coater blade width twice for employing corresponds essentially to makes.